This invention relates to a process for the preparation of aldehydes by hydroformylation of unsaturated organic compounds in the presence of a Group VIII metal and selected polymeric phosphite ligands. The invention also relates to composition of selected hydroformylation catalysts derived from polymeric phosphite ligands and Group VIII metal.
Phosphorus-based ligands are ubiquitous in catalysis and are used for a number of commerically important chemical transformations. Phosphorus-based ligands commonly encountered in catalysis include phosphines and phosphites. These ligands include monophosphine and monophosphite ligands, which are compounds that contain a single phosphorus atom that serves as a donor to a transition metal, and bisphosphine, bisphosphite, and bis(phosphorus) ligands, which contain two phosphorus donor atoms and normally form cyclic chelate structures with transition metals.
An industrially important catalytic reaction using phosphorus-based ligands of particular importance is olefin hydroformylation. Phosphite ligands are particularly good ligands for these reactions. For example, U.S. Pat. No. 5,235,113 describes a hydroformylation process in which an organic bidentate ligand containing two phosphorus atoms linked with an organic dihydroxyl bridging group is used in a homogeneous hydroformylation catalyst system also comprising rhodium. See also Cuny et al., J. Am. Chem. Soc., 1993, 115, 2066; U.S. Pat. Nos. 4,769,498; 4,668,651; 4,885,401; 5,113,022; 5,059,710; 5,235,113; 5,264,616; 4,885,401; and published international applications WO-A-9303839 and WO-A-9518089.
Hydroformylation processes involving organic bidentate ligands containing two trivalent phosphorus atoms, in which the two phosphorous atoms are linked with a 2,2xe2x80x2-dihydroxyl-1,1xe2x80x2-binaphthalene bridging group, are described in U.S. Pat. No. 5,874,641 and the prior art referenced therein. U.S. Pat. No. 5,874,641 describes ligands containing substituents such as esters or ketones on the 3,3xe2x80x2-positions of the 2,2xe2x80x2-dihydroxyl-1,1xe2x80x2-binaphthalene bridging group. Such ligands provide reasonably good selectivity in the hydroformylation of internal olefins to terminal aldehydes.
Recovery of the ligand and catalyst is important for a successful process. Typical separation procedures to remove the product(s) from the catalyst and ligand involve extraction with an immiscible solvent or distillation. It is usually difficult to recover the catalyst and ligand quantitatively. For instance, distillation of a volatile product from a non-volatile catalyst results in thermal degradation of the catalyst. Similarly, extraction results in some loss of catalyst into the product phase. For extraction, one would like to be able to tune the solubility of the ligand and catalyst to disfavor solubility in the product phase. These ligands and metals are often very expensive and thus it is important to keep such losses to a minimum for a commercially viable process.
One method to solve the problem of catalyst and product separation is to attach the catalyst to an insoluble support. Examples of this approach have been previously described, and general references on this subject can be found in xe2x80x9cSupported Metal Complexesxe2x80x9d, D. Reidel Publishing, 1985, Acta Polymer., 1996, 47, 1; Comprehensive Organometallic Chemistry, Pergamon Press, 1982,553; J. of Mol. Catal. A, 104, 1995, 17-85 and Macromol. Symp. 80, 1994, 241. Specifically, monophosphine and monophosphite ligands attached to solid supports are described in these references. Bisphosphine ligands have also been attached to solid supports and used for catalysis, as described in for example U.S. Pat. No. 5,432,289; J. Mol. Catal. A, 112, 1996, 217; and J. Chem. Soc., Chem. Commun., 1996, 653. The solid support in these prior art examples can be organic, e.g., a polymer resin, or inorganic in nature.
Polymer-supported multidentate phosphorus ligands may be prepared by a variety of methods known in the art. See U.S. Pat. Nos. 4,769,498 and 4,668,651 and published international applications WO9303839 and WO9906146 and EP 0864577 A2 and EP0877029 A2. These prior art disclose side-chain polymers containing multidentate phosphorus ligands as pendant groups.
The present invention involves another approach to improving recovery of the catalyst by providing polymeric forms of the bidentate ligands themselves.
There is an increasing need to develop a catalytic process in which the loss of catalyst composition can be substantially reduced during separation of product from the catalyst. An object of the invention is to provide a hydroformylation process. An advantage of the invention is that varying the molecular weight and degree of branching can control the solubility of the catalyst composition. Another advantage of the invention is that the catalyst composition can be substantially recovered by, for example, filtration. Other objects and advantages of the present invention will become apparent as the invention is more fully disclosed below.
According to a first embodiment of the invention, a process is provided. The process comprises contacting, in the presence of a catalyst, an unsaturated organic compound with a fluid containing hydrogen and carbon monoxide under a condition sufficient to produce an aldehyde wherein said catalyst is selected from the group consisting of catalyst A, catalyst B, and combinations thereof. Catalyst A comprises a Group VIII metal and polymer A that comprises repeat units derived from (1) a carbonyl compound, (2) a monomer, and (3) phosphochloridite. Catalyst B comprises a Group VIII metal and polymer B which comprises repeat units derived from (1) phosphorus trichloride, (2) a polyhydric alcohol, and (3) an aromatic diol.
According to a second embodiment of the invention, a composition is provided that comprises a Group VIII metal and a phosphite polymeric composition selected from the group consisting of polymer A, polymer B, and combinations thereof; the polymer A comprises repeat units derived from (1) a carbonyl compound, (2) a monomer, and (3) phosphochloridite; and the polymer B comprises repeat units derived from (1) phosphorus trichloride, (2) a polyhydric alcohol, and (3) an aromatic diol.
The polymeric phosphite composition is also referred to herein as ligand. The ligands suitable for use in the process of the invention are polymer A and polymer B. Polymer A comprises repeat units derived from (1) a carbonyl compound, (2) a monomer, and (3) phosphorochloridite. The monomer is selected from the group consisting of a first polyhydric alcohol, an amine, and combinations thereof. Polymer B comprises repeat units derived from (1) phosphorus trichloride, (2) a second polyhydric alcohol, and (3) an aromatic diol.
The carbonyl compound has the formula of (R1O2C)m(OH)xe2x80x94Ar1xe2x80x94(OH)(CO2R1)m, (R1O2C)m(OH)xe2x80x94Ar2xe2x80x94A2xe2x80x94Ar2xe2x80x94(OH)(CO2R1)m, (R1O2C)m(OH)xe2x80x94Ar2xe2x80x94Ar2xe2x80x94(OH)(CO2R1)m, and combinations of two or more thereof;
The term xe2x80x9cpolyhydric alcoholxe2x80x9d used herein refers to, unless otherwise indicated, a molecule having two or more hydroxyl groups. Generally a polyhydric alcohol can be selected from the group consisting of dialcohols, trialcohols, tetraalcohols, and combinations of two or more thereof.
The first polyhydric alcohol has the formula selected from the group consisting of (HO)mxe2x80x94A1xe2x80x94(OH)m, (HO)mxe2x80x94Ar2xe2x80x94A1xe2x80x94Ar2xe2x80x94(OH)m, (HO)mxe2x80x94Ar2xe2x80x94(O)xe2x80x94A1xe2x80x94(O)xe2x80x94Ar2xe2x80x94(OH)m, (HO)mxe2x80x94(A1xe2x80x94O)pxe2x80x94A1xe2x80x94(OH)m,(HOxe2x80x94A1)m(OH)xe2x80x94Ar1xe2x80x94(OH)(A1xe2x80x94OH)m, (HOxe2x80x94A1)m(OH)xe2x80x94Ar2xe2x80x94A2xe2x80x94Ar2xe2x80x94(OH)(A1xe2x80x94OH)m, (HOxe2x80x94A1)m(OH)xe2x80x94Ar2xe2x80x94Ar2xe2x80x94(OH)(A1xe2x80x94OH)m, (HO)mxe2x80x94Ar2xe2x80x94(Oxe2x80x94A1)pxe2x80x94Oxe2x80x94Ar2xe2x80x94(OH)m, (OH)mxe2x80x94Ar2xe2x80x94Ar2xe2x80x94(OH)m, (OH)mxe2x80x94Ar2xe2x80x94A2xe2x80x94Ar2xe2x80x94(OH)m, (HO)mxe2x80x94Ar2xe2x80x94A1xe2x80x94C(O)xe2x80x94Oxe2x80x94A1xe2x80x94Oxe2x80x94C(O)xe2x80x94A1xe2x80x94Ar2xe2x80x94(OH)m, (OH)xe2x80x94Ar1(OH), and combinations of two or more thereof.
Each Ar1 is selected from the group consisting of C6 to C40 phenylene group, C12 to C40 biphenylene group, C10 to C40 naphthylene group, C20 to C40 binaphthylene group, and combinations of two or more thereof.
Each Ar2 is independently selected from the group consisting of C6 to C40 phenylene group, C10 to C40 naphthylene group, and combinations thereof.
Each A1 is independently selected from the group consisting of C1 to C12 alkylene groups.
Each A2 is independently selected from the group consisting of xe2x80x94C(R1)(R1), xe2x80x94Oxe2x80x94,xe2x80x94N(R1)xe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94S(O)2xe2x80x94, xe2x80x94S(O)xe2x80x94, and combinations of two or more thereof.
Each R1 is independently selected from the group consisting of hydrogen, C1 to C12 alkyl or cycloalkyl group, C6 to C20 aryl group, and combinations of two or more thereof.
Each R2 is independently selected from the group consisting of hydrogen, C1 to C12 alkyl or cycloalkyl group, acetal having 2 to about 20 carbon atoms, ketal having 2 to about 20 carbon atoms, xe2x80x94OR3, xe2x80x94CO2R3, C6 to C20 aryl group, F, Cl, xe2x80x94NO2, xe2x80x94SO3R3, xe2x80x94CN, perhaloalkyl having 1 to about 12 carbon atoms, xe2x80x94S(O)R3, xe2x80x94S(O)2R3, xe2x80x94CHO, xe2x80x94C(O)R3, cyclic ether having 2 to about 10 carbon atoms, xe2x80x94A1Z, and combinations of two or more thereof;
each Z is selected from the group consisting of xe2x80x94CO2R3, xe2x80x94CHO, xe2x80x94C(O)R3, xe2x80x94C(O)SR3, xe2x80x94SR3, xe2x80x94C(O)NR1R1, xe2x80x94OC(O)R3, xe2x80x94OC(O)OR3, xe2x80x94Nxe2x95x90CR1R1, xe2x80x94C(R1)xe2x95x90NR1, xe2x80x94C(R1)xe2x95x90Nxe2x80x94Oxe2x80x94R1, xe2x80x94P(O)(OR3)(OR3), xe2x80x94S(O)2R3, xe2x80x94S(O)R3xe2x80x94C(O)OC(O)R3, xe2x80x94NR3CO2R3, xe2x80x94NR3C(O)NR1R1, F, Cl, xe2x80x94NO2, xe2x80x94SO3R3, perhaloalkyl, xe2x80x94CN, and combinations of two or more thereof;
Each R3 is independently selected from the group consisting of C1 to C12 alkyl or cycloalkyl group, C6 to C20 aryl group, and combinations thereof.
Each m is independently a number in the range of from 1 to 2.
Each p is independently a number in the range of from 1 to 10.
The presently preferred carbonyl compounds are diesters, diacids, or combinations thereof.
Examples of suitable diesters or diacids include, but are not limited to those shown below: 
in which each R1 is independently selected from the group consisting of hydrogen, C1 to C12 alkyl or cycloalkyl group, C6 to C20 aryl group, and combinations of two or more thereof. The other positions on the aromatic rings can also be substituted with an alkyl group, ether group, ester group, or combinations thereof.
Specific examples of suitable diesters or diacids include, but are not limited to, dialkyl 2,2xe2x80x2-dihydroxyl-1,1xe2x80x2-binaphthalene-3,3xe2x80x2-dicarboxylate, dialkyl 2,2xe2x80x2-dihydroxyl-1,1xe2x80x2-biphenyl-3,3xe2x80x2-dicarboxylate, 2,2xe2x80x2-dihydroxy-biphenyl-3,3xe2x80x2-dicarboxylic acid, 2,2xe2x80x2-dihydroxy-1,1xe2x80x2-binaphthyl-3,3xe2x80x2-dicarboxylic acid and combinations of two or more thereof.
The carbonyl compounds illustrated above can also be blended with one or more second carbonyl compounds such as, for examples, (R1O2C)mxe2x80x94Ar1xe2x80x94(CO2R1)m, (R1O2C)mxe2x80x94A1xe2x80x94(CO2R1)m, (R1O2C)mxe2x80x94Ar2xe2x80x94A1xe2x80x94Ar2xe2x80x94(CO2R1)m, (R1O2C)mxe2x80x94Ar2xe2x80x94(O)xe2x80x94A1xe2x80x94(O)xe2x80x94Ar2xe2x80x94(CO2R1)m, (R1O2C)mxe2x80x94(A1xe2x80x94O)pxe2x80x94A1(CO2R1)m, and combinations of two or more thereof.
Examples of the second carbonyl compounds that can be blended are terephthalic acid, isophthalic acid, phthalic acid, dimethyl isophthalate, dimethyl phthalate, dimethyl terephthalate.
The first polyhydric alcohol can be aromatic as in a phenol or aliphatic as in an alkyl alcohol and can contain two aromatic alcohols, two aliphatic alcohols, or one of each. The alcohol has the formula disclosed in the above.
Examples of the first polyhydric alcohols include, but are not limited to, those illustrated as follows. 
Other examples of the first polyhydric alcohols are hexa(ethylene glycol), 1,3-propananediol, tetra(ethylene glycol), 1,4-cyclohexanediol, 2,6-dihydroxynaphthalene, or combinations of two or more thereof.
In addition to the polyhydric alcohols shown above, compounds containing three or more hydroxy groups can be used. An example of such compound is 1,3,5-benzene tricarboxylic acid.
The monomer can also be an amine selected from the group consisting of diamines, triamines, tetraamines, and combinations of two or more thereof. The amine can be primary or secondary aliphatic amine. Some examples are 1,6-hexanediamine, N,Nxe2x80x2-dimethylhexanediamine, 1,4-butanediamine, and combinations of two or more thereof.
The phosphochloridite has the formula of CIP(Oxe2x80x94Ar2xe2x80x94R2)2, where the Ar2 groups can be unlinked or linked directly to each other or with a group A2 and the R2 group is preferably ortho to the oxygen.
Examples of phosphorochloridite include, but are not limited to, those shown below. 
in which the other positions on the aromatic ring, i.e., para or meta to the oxygen atom, can also be substituted with alkyl, ether or ester groups, or combinations of two or more thereof.
Polymer A can be produced by any means known to one skilled in the art. A process that can be used for producing polymer A disclosed above comprises (1) contacting a carbonyl compound and a monomer under a condition sufficient to produce an intermediate and (2) contacting the intermediate with phosphorochloridite under a condition effective to produce the composition disclosed in the first embodiment of the invention.
The definition and scope of the carbonyl compound, monomer, and phosphochloridite are the same as those disclosed above and, for the interest of brevity, the description of which is omitted herein.
In the first step of the process, a carbonyl compound disclosed above is contacted with a monomer disclosed above to produce an intermediate that can be a polyester or a polyamide. The contacting can be carried out with any molar ratio of the monomer to carbonyl compound so long as the ratio is sufficient to produce the intermediate. The ratio generally can be in the range of from about 0.1:1 to about 10:1, preferably about 0.5:1 to about 5:1, and most preferably about 1:1 to about 2:1. Generally the process can be carried out with either an excess of monomer or equimolar amount of monomer to carbonyl compound. The ratio of reactive ester or acid to reactive alcohol or amine of one is most preferred.
Alternatively, the carbonyl compound can be combined with a second or other carbonyl compounds disclosed above. Additional examples of the second carbonyl compounds include, but are not limited to (R1O2C)mxe2x80x94Ar1xe2x80x94(CO2R1)m, (R1O2C)mxe2x80x94A1xe2x80x94(CO2R1)m, (R1O2C)mxe2x80x94Ar2xe2x80x94A1xe2x80x94Ar2xe2x80x94(CO2R1)m, (R1O2C)mxe2x80x94Ar2xe2x80x94(O)xe2x80x94A1xe2x80x94(O)xe2x80x94Ar2xe2x80x94(CO2R1)m, (R1O2C)mxe2x80x94(A1xe2x80x94O)pxe2x80x94A1xe2x80x94(CO2R1)m, and combinations of two or more thereof.
The contacting can be carried out under any condition as long as the condition is sufficient to effect the production of the intermediate. Generally it includes a temperature in the range of from about 100xc2x0 C. to about 450xc2x0 C., preferably about 150xc2x0 C. to about 350xc2x0 C., and most preferably 180xc2x0 C. to 270xc2x0 C., under any pressure that can accommodate the temperature range, and for a sufficient time of about 1 minute to about 24 hours. The contacting can also be carried out neat or with an inert solvent such as tetraglyme.
The resulting intermediate can be then contacted with a phosphochloridite disclosed above to form the polymeric phosphite ligand. The contacting can be carried out, if desired, in a solvent such as toluene or tetrhydrofuran under a condition sufficient to effect the production of the composition. The contacting can be carried out in the presence of a base such as an organic base. The addition of base results in the formation of a salt formed by neutralizing HCl. Suitable bases can be organic amines. Especially preferred are trialkylamines. The most preferred bases are selected from the group consisting of tributylamine, benzyldimethylamine, triethylamine, and diisopropylmethylamine. The contacting condition can include a temperature in the range of from about xe2x88x9250xc2x0 C. to about 150xc2x0 C., preferably about xe2x88x9240xc2x0 C. to about 100xc2x0 C., and most preferably, xe2x88x9230xc2x0 C. to 80xc2x0 C., under any pressure that can accommodate the temperature range, and for a sufficient time of about 1 minute to about 24 hours.
The molar ratio of the phosphochloridite to the alcohol group of the intermediate, can range from about 10:1 to about 0.5: 1, preferably about 1:1.
The phosphorochloridite can be prepared by contacting at a temperature between about xe2x88x9240xc2x0 C. and 10xc2x0 C. about one molar equivalent of PCl3 with about two molar equivalents of substituted phenol in the absence of a base such as an organic base. The resulting solution can be then contacted with at least two equivalents of a base such as an organic base to produce a phosphorochloridite. When the substituted phenols are replaced with substituted biphenol or substituted alkylidenebisphenol, the phosphorochloridite can be similarly prepared from initially contacting about one molar equivalent of PCl3 with about one molar equivalent of substituted biphenol or substituted alkylidenebisphenol between about xe2x88x9240xc2x0 C. and 10xc2x0 C. in the absence of an organic base. The resulting solution is then contacted with at least two equivalents of a base such as an organic base to produce a phosphorochloridite.
When preparing the phosphorochloridite in the above manner, it is desirable to maintain temperature in the xe2x88x9240xc2x0 C. and 10xc2x0 C. range during the base addition. The addition of base results in the formation of an insoluble salt formed by neutralizing HCl, the reaction mixture can become a thick slurry. Such a slurry can create problems in achieving good mixing of base, which can be important in avoiding temperature gradients in the reaction mixture that can decrease yield of the desired product. It is desirable, therefore, that the reaction be conducted with vigorous stirring or other agitation to allow effective removal of heat from the reaction mixture. Cooling to the disclosed temperature range can be accomplished by well-known techniques in the art.
The phosphochloridite can be prepared by a variety of other methods known to in the art, for example. One method involves treating phenols with PCl3, such as described in Polymer, 1992, 33, 161; Inorg. Syn. 1996, 8, 68; U.S. Pat. No. 5,210,260; WO9622968 and Z. Anorg Allg Chem. 1986, 535, 221.
When the phosphorochloridite cannot be prepared in good yield from PCl3, the preferred method involves the treatment of N,N-dialkyl diarylphosphoramidite derivatives with HCl. When the phosphorochloridite cannot be prepared in good yield from PCl3, the preferred method involves the treatment of N,N-dialkyl diarylphosphoramidite derivatives with HCl. The N,N-dialkyl diarylphosphoramidite is of the form (R9)2NP(aryloxy)2 where R9 is a C1 to C4 alkyl group, and can be obtained by reacting phenol or substituted phenol with (R9)2NPCl2 by methods known in the art, such as described in WO9622968, U.S. Pat. Nos. 5,710,306, and 5,821,378. The N,N-dialkyl diarylphosphoramidites may be prepared, for example, as described in Tet. Lett., 1993, 34,6451; Synthesis, 1988, 2, 142-144, and Aust. J. Chem., 1991, 44, 233.
Non limiting examples of the production of the intermediate, i.e., polyester or polyamide, are shown below. 
The molecular weight of the polymer depicted above can be adjusted according to need or desire by adjusting the conditions of the process or the moles of carbonyl compound, monomer, or both.
Polymer A can be combined with a Group VIII metal to produce a catalyst composition A. The term xe2x80x9cmetalxe2x80x9d used herein refers to transition metal, transition metal compound, transition metal complex, or combinations thereof. The term xe2x80x9cGroup VIIIxe2x80x9d refers to the ACS version of the Periodic Table of the Elements, 67th edition (1986-1987), CRC Handbook of Chemistry and Physics, Press, Boca Raton, Fla. For the catalyst composition, the polymer component is also referred to herein as a ligand.
Generally, a Group VIII metal is combined with a polymer disclosed above to produce the desired catalyst. Preferred Group VIII metals are rhodium, iridium, ruthenium, platinum, and combinations of two or more thereof. The most preferred is rhodium. The Group VIII metal is provided in the form of a compound, such as a hydride, halide, organic acid salt, ketonate, inorganic acid salt, oxide, carbonyl compound, amine compound, or combinations of two or more thereof. Preferred Group VIII metal compounds are Ir4(CO)12, IrSO4, RhCl3, Rh(NO3)3, Rh(OAc)3, Rh2O3, Rh(acac)(CO)2, [Rh(OAc)(COD)]2, Rh4(CO)12, Rh6(CO)16, RhH(CO)(Ph3P)3, [Rh(OAc)(CO)2]2, [RhCl(COD)]2, and combinations of two or more thereof (xe2x80x9cacacxe2x80x9d is an acetylacetonate group; xe2x80x9cOAcxe2x80x9d is an acetyl group; xe2x80x9cCODxe2x80x9d is 1,5-cyclooctadiene; and xe2x80x9cPhxe2x80x9d is a phenyl group). However, it should be noted that the Group VIII metal compounds are not necessarily limited to the above listed compounds. The rhodium compounds, suitable for hydroformylation, can be prepared or generated according to techniques well known in the art, as described, for example, in WO 95 30680, U.S. Pat. No. 3,907,847, and J. Amer. Chem. Soc., 115, 2066, 1993. Rhodium compounds that contain ligands, which can be displaced by the present multidentate phosphite ligands, are a preferred source of rhodium. Examples of such preferred rhodium compounds are Rh(CO)2 (acac), Rh(CO)2(C4H9COCHCO-t-C4H9), Rh2O3, Rh4(CO)12, Rh6(CO)16, Rh(O2CCH3)2, Rh(2-ethylhexanoate), and combinations of two or more thereof.
The amount of transition metal can be any amount so long as favorable results can be obtained with respect to catalyst activity and process economy, when used as a catalyst. In general, the molar ratio of phosphorus ligand to transition metal generally can be from about 1:1 to about 100:1, preferably from about 1:1 to about 20:1 (moles phosphorus per mole metal).
Polymer B comprises repeat units derived from (1) phosphorus trichloride, (2) a second polyhydric alcohol, and (3) an aromatic diol . The PCl3 can be blended with Cl2P(OAr3) or ClP(OAr3)2 wherein Ar3 is C6 to C24 aryl in which the aryl group can be substituted with alkyl, aryl, ether and ester.
The location of the OH groups is preferably placed such that the reaction with PCl3 will not lead to predominate formation of monodentate phosphites.
Preferred second polyhydric alcohol has the formula selected from the group consisting of (R4)(HO)mxe2x80x94Ar2xe2x80x94A1xe2x80x94Ar2xe2x80x94(OH)m(R4), (R4)(HO)mxe2x80x94Ar2xe2x80x94(Oxe2x80x94A1)pxe2x80x94Oxe2x80x94Ar2xe2x80x94(OH)m(R4), (R4)(OH)mxe2x80x94Ar2xe2x80x94Ar2xe2x80x94(OH)m(R4), (R4)(OH)mxe2x80x94Ar2xe2x80x94A2xe2x80x94Ar2xe2x80x94(OH)m(R4), (R4)(HO)mxe2x80x94Ar2xe2x80x94A1xe2x80x94C(O)xe2x80x94Oxe2x80x94A1xe2x80x94Oxe2x80x94C(O)xe2x80x94A1xe2x80x94Ar2xe2x80x94(OH)m(R4), (R4)(OH)mxe2x80x94Ar1xe2x80x94(OH)m(R4), and combinations thereof; when R4 is not hydrogen and located ortho to the OH group, the other substituent ortho to the OH group is hydrogen;
each R4 is independently selected from the group consisting of hydrogen, C1 to C12 alkyl or cycloalkyl group, acetal, ketal, xe2x80x94OR3, xe2x80x94CO2R3, C6 to C20 aryl group, xe2x80x94SiR3, xe2x80x94NO2, xe2x80x94SO3R3, xe2x80x94S(O)R3, xe2x80x94S(O)2R3, xe2x80x94CHO, xe2x80x94C(O)R3, F, Cl, xe2x80x94CN, or perhaloalkyl, xe2x80x94C(O)N(R3)(R3), xe2x80x94A1Z, and combinations of two or more thereof;
each Z is xe2x80x94CO2R3, xe2x80x94CHO, xe2x80x94C(O)R3, xe2x80x94C(O)SR3, xe2x80x94SR3, xe2x80x94C(O)NR1R1, xe2x80x94OC(O)R3, xe2x80x94OC(O)OR3, xe2x80x94Nxe2x95x90CR1R1, xe2x80x94C(R1)xe2x95x90NR1, xe2x80x94C(R1)xe2x95x90Nxe2x80x94Oxe2x80x94R1, xe2x80x94P(O)(OR3)(OR3), xe2x80x94S(O)2R3,xe2x80x94S(O)R3, xe2x80x94C(O)OC(O)R3, xe2x80x94NR3CO2R3, xe2x80x94NR3C(O)NR1R1, F, Cl, xe2x80x94NO2, xe2x80x94SO3R3, xe2x80x94CN or combinations thereof;
each R3 is independently selected from the group consisting of C1 to C12 alkyl or cycloalkyl group, C6 to C20 aryl group.
When R4 is independently selected from the group consisting of C1 to C12 alkyl or cycloalkyl group, acetal, ketal, xe2x80x94OR3, xe2x80x94CO2R3, C6 to C20 aryl group, xe2x80x94SiR3, xe2x80x94SO3R3, xe2x80x94S(O)R3, xe2x80x94S(O)2R3, perhaloalkyl, xe2x80x94C(O)N(R3)(R3), xe2x80x94A1CO2R3, xe2x80x94A1OR3; the polyhydric alcohol can be (OH)mAr1xe2x80x94R4xe2x80x94R4xe2x80x94Ar1(OH)m, (OH)mAr1xe2x80x94R4xe2x80x94A1xe2x80x94R4xe2x80x94Ar1(OH)m, or combinations of two or more thereof.
All aryl groups, arylene groups, alkyl groups, alkylene groups, esters, ethers, acetals, and ketal disclosed in the invention can be substituted with one or more aryl groups, arylene groups, alkyl groups, alkylene groups, ethers, esters, acetals, and ketals.
Some representative second polyhydric alcohols include, but are not limited to, those shown in the following formulas. 
in which R1 and R4 are the same as disclosed above. The other positions on the aromatic ring, preferably para or meta to the oxygen atom, can also be substituted with alkyl, ether or ester groups.
Some representative examples are 6,6xe2x80x2-dihydroxy-4,4,4xe2x80x2, 7,7,7xe2x80x2-hexamethyl bis-2,2xe2x80x2-spirochroman, 2,2xe2x80x2-diallylbisphenolA, bisphenol A, 4,4xe2x80x2-(1-methylethylidene)bis(2-(1-methylpropyl)phenol), 4,4xe2x80x2-thiophenol, 4,4xe2x80x2-dihydroxydiphenylsulfone, 4,4xe2x80x2-sulfonylbis(2-methylphenol), bis(4-hydroxy-3-methylphenyl)sulfide, 2,2xe2x80x2-dis(4-hydroxy-3-methylphenyl)propane, 4,4xe2x80x2-ethylidenebis(2,5-dimethylphenol), 4,4xe2x80x2-propylidenebis(2,5-dimethylphenol), 4,4xe2x80x2-benzylidenebis(2,5-dimethylphenol), 4,4xe2x80x2-ethylidenebis(2-isopropyl-5-methylphenol), and combinations of two or more thereof.
These second polyhydric alcohols can be produced by those skilled in the art. For example, the diacetal can be prepared by refluxing di(trimethylolpropane) with salicylaldehyde with oxalic acid as catalyst. For references for preparing acetal from acid catalyzed reaction of an aldehyde and an alcohol, see Tetrahedron, 1996, 14599; Tet. Lett., 1989, 1609; Tetrahedron, 1990, 3315. 1,3-bis(2-hyroxyphenoxy)propane was prepared by a literature procedure, J. Org. Chem., 48, 1983,4867. 4,4xe2x80x2-ethylidenebis(2,5-dimethylphenol); 4,4xe2x80x2-propylidenebis(2,5-dimethylphenol); 4,4xe2x80x2-benzylidenebis(2,5-dimethylphenol); and 4,4xe2x80x2-ethylidenebis(2-isopropyl-5-methylphenol) can be prepared according to Bull. Chem. Soc. Jpn., 62, 3603 (1989).
In addition to the polyhydric alcohols shown above, compounds containing three or more phenolic groups can be used. Representative examples are shown below: 
in which R4 are the same as disclosed above. The other positions on the aromatic ring, preferably para or meta to the oxygen atom, can also be substituted with alkyl, ether or ester groups.
The aromatic diol has the following formula 
wherein:
each R4 is independently selected from the group consisting of hydrogen, C1 to C12 alkyl or cycloalkyl group, acetal, ketal, xe2x80x94OR3, xe2x80x94CO2R3, C6 to C20 aryl group, xe2x80x94SiR3, xe2x80x94NO2, xe2x80x94SO3R3, xe2x80x94S(O)R3, xe2x80x94S(O)2R3, xe2x80x94CHO, xe2x80x94C(O)R3, xe2x80x94F, xe2x80x94Cl, xe2x80x94CN, xe2x80x94CF3, xe2x80x94C(O)N(R3)(R3), xe2x80x94A1Z, and combinations of two or more thereof;
Z is xe2x80x94CO2R3, xe2x80x94CHO, xe2x80x94C(O)R3, xe2x80x94C(O)SR3, xe2x80x94SR3, xe2x80x94C(O)NR1R1, xe2x80x94OC(O)R3, xe2x80x94OC(O)OR3, xe2x80x94Nxe2x95x90CR1R1, xe2x80x94C(R1)xe2x95x90NR1, xe2x80x94C(R1)xe2x95x90Nxe2x80x94Oxe2x80x94R1, xe2x80x94P(O)(OR3)(OR3), xe2x80x94S(O)2R3, xe2x80x94S(O)R3, xe2x80x94C(O)OC(O)R3, xe2x80x94NR3CO2R3, xe2x80x94NR3C(O)NR1R1, F, Cl, xe2x80x94NO2, xe2x80x94SO3R3, xe2x80x94CN, or combinations of two or more thereof;
each R3 is independently selected from the group consisting of C1 to C12 alkyl or cycloalkyl group, C6 to C20 aryl group;
each R5 independently is H, F, Cl, C1 to C12 alkyl or cycloalkyl, C6 to C20 aryl, xe2x80x94OR3, xe2x80x94CO2R3, xe2x80x94C(O)R3, xe2x80x94CHO, xe2x80x94CN, xe2x80x94CF3, or combinations of two or more thereof;
each R6 independently is H, C1 to C12 alkyl or cycloalkyl, C6 to C20 aryl, or combinations of two or more thereof; and
each R7 independently is H, C1 to C12 alkyl or cycloalkyl, C6 to C20 aryl, or combinations of two or more thereof.
These aromatic diols can be prepared by any means known to those skilled in the art. Examples include, but are not limited to, 2,2xe2x80x2-dihydroxy-3,3xe2x80x2-dimethoxy-5,5xe2x80x2-dimethyl-1,1xe2x80x2-biphenylene which can be prepared using the procedure described in Phytochemistry, 27, 1988, 3008; 2,2xe2x80x2-ethylidenebis(4,6-dimethylphenol) which can be prepared according to Bull. Chem. Soc. Jpn., 1989, 62, 3603; 3,3xe2x80x2-dimethoxy-2,2xe2x80x2-dihydroxy-1,1xe2x80x2-binaphthalene which can be prepared by the procedure of Recl. Trav. Chim. Pays. Bas., 1993, 112, 216; diphenyl 2,2xe2x80x2-dihydroxy-1,1xe2x80x2-binaphthalene-3,3xe2x80x2-dicarboxylate which can be prepared by the procedure described in Tetrahedron Lett., 1990, 413; 3,3xe2x80x2,5,5xe2x80x2-tetrmethyl-2,2xe2x80x2-biphenol and 3,3xe2x80x2,4,4xe2x80x2,6,6xe2x80x2-hexamethyl-2,2xe2x80x2-biphenol which can be prepared using the procedure described in J. Org. Chem., 1963, 28, 1063; and 3,3xe2x80x2-dimethyl-2,2xe2x80x2-dihydroxydiphenylmethane which can be prepared using the procedure described in Synthesis, 1981, 2, 143.
These aromatic diols can be incorporated in a polymer as in the polyester and polyamide described above for polymer A. These polymers containing the aromatic diols can be used in polymer B of the invention.
The solubilities of these polymeric phosphite ligands above generally depend on the molecular weight of the polymer and degree of branching. For soluble polymeric system, separation can therefore be done by extraction. With insoluble polymeric systems, the catalyst can be placed in fixed beds or separated by filtration from a reaction mixture. Alternatively, the solubility of the polymer can be adjusted to be soluble in the reactants and insoluble in the products. Thus, the reaction can be carried out homogeneously to obtain high conversion. The polymeric catalyst can then be separated by easy means such as decantation or filtration.
Polymer B can also form a catalyst composition B when combined with a catalytically active metal such as Group VIII metal. The metal can be the same as that above and the description of which is omitted herein for the interest of brevity.
It is presently preferred that polymer B is produced by a process which comprises (1) contacting phosphorus trichloride and a second polyhydric alcohol under a condition sufficient to produce a phosphorus-containing polymer and (2) contacting the phosphorus-containing polymer with an aromatic diol.
The definition and scope of the second polyhydric alcohol and aromatic diol are the same as those disclosed above.
In the first step of the process, a phosphorus-containing polymer with Pxe2x80x94Cl bonds is prepared. The polymer containing phosphorochloridite can be prepared by treating one molar equivalent of PCl3 with about two molar equivalent of reactive hydroxy groups in the second polyhydric alcohol in the absence of an organic base. The resulting solution is then treated with at least two equivalents of a base such as, for example, an organic base to produce a polymer containing phosphorochloridite. Suitable bases are organic amines disclosed above. The condition can include a temperature in the range of from about xe2x88x9240xc2x0 C. to about 25xc2x0 C., preferably about xe2x88x9220xc2x0 C. to about 10xc2x0 C., under a pressure that can accommodate the temperature, and for a sufficient period of time which can be about 1 minute to about 24 hours. The PCl3 can be blended with Cl2P(OAr3) and ClP(OAr3)2 wherein Ar3 is a C6 to C24 aryl group in which the aryl group can be substituted with alkyl, aryl, ether and ester.
The molar ratio of phosphorus trichloride to the alcohol can be any ratio so long as the ratio is sufficient to effect the production of a desired phosphorus-containing polymer. With or without blending with Cl2P(OAr3) and ClP(OAr3)2, generally the molar ratio of PCl3 to reactive xe2x80x94OH groups can range from about 10:1 to about 1:3; preferably 1:2.
According to the invention, the phosphorus-containing polymer can be alternatively produced by contacting an N,N-dialkyl dichlorophosphoramidite with the second polyhydric alcohol to produce a polymeric phosphoramidite followed by contacting the polymeric phosphoramidite with an acid such as, for example, hydrochloric acid to produce the phosphorus-cotaining polymer such as, for example,polymeric phosphorochloridite. Generally any N,N-dialkyl dichlorophosphoramidite known to one skilled in the art can be used. Each of the alkyl group can contain 1 to about 20, preferably 1 to about 10 carbon atoms.
The molecular weight of the phosphorus-containing polymer can be modified by further contact with an aromatic diol that will react with unreacted Pxe2x80x94Cl bonds. The contacting of the phosphorus-containing polymer with the aromatic diol can be carried out under a condition sufficient to produce a polymer containing a phosphite group. The contacting of the polymer containing phosphorochloridite with an aromatic diol can be carried out in the presence of a base disclosed above. Sufficient base can be used in steps (1) and (2) such that all generated HCl can be neutralized. The condition can include a temperature in the range of from about xe2x88x9250xc2x0 C. to about 150xc2x0 C., preferably about xe2x88x9240xc2x0 C. to about 100xc2x0 C., and most preferably, xe2x88x9230xc2x0 C. to 80xc2x0 C. under a pressure that can accommodate the temperature, and for a sufficient period of time which can be about 1 minute to about 24 hours.
The molar ratio of aromatic diol to unreacted Pxe2x80x94Cl can be any ratio so long as the ratio is sufficient to effect the production of a desired phosphorus-containing polymer. The ratio generally can be in the range of from about 2:1 to about 1:2. It is most preferred that about equal mole of OH groups in the aromatic diol and the Pxe2x80x94Cl bonds in the phosphorus-containing polymer be used.
The catalyst compositions A and B are useful for the hydroformylation of unsaturated organic compounds in which an aldehyde compound can be prepared.
The term xe2x80x9cfluidxe2x80x9d refers to liquid, gas, or combinations thereof. A fluid comprising hydrogen can contain about 1 to about 100% hydrogen. Similarly, a fluid comprising carbon monoxide can contain about 1 to about 100% CO. It is presently preferred that a 1:1 ratio of CO and hydrogen is used.
The reactant of the present process is an unsaturated organic compound preferably 2 to about 20 carbon atoms. Examples of suitable unsaturated organic compounds include, but are not limited to, linear terminal olefinic hydrocarbons, for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-nonene, 1-decene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and 1-dodecene; branched terminal olefinic hydrocarbons, for example, isobutene and 2- methyl-1-butene; linear internal olefinic hydrocarbons, for example, cis- and trans-2-butene, cis- and trans-2-hexene, cis- and trans-2-octene, cis- and trans-3-octene; branched internal olefinic hydrocarbons, for example, 2,3-dimethyl-2-butene, 2-methyl-2-butene and 2-methyl-2-pentene; terminal olefinic hydrocarbons; internal olefinic hydrocarbon mixtures; for example, octenes, prepared by dimerization of butenes; cyclic olefins, for example, cyclohexene, cyclooctene; and combinatins of two or more thereof.
Examples of suitable olefinic compounds also include those substituted with an unsaturated hydrocarbon group, including olefinic compounds containing an aromatic substituent such as styrene, alpha-methylstyrene and allylbenzene.
The unsaturated organic compound can also be substituted with one or more functional groups containing a heteroatom, such as oxygen, sulfur, nitrogen or phosphorus. Examples of these heteroatom-substituted ethylenically unsaturated organic compounds include vinyl methyl ether, methyl oleate, oleyl alcohol, 3-pentenenitrile, 4-pentenenitrile, 3-pentenoic acid, 4-pentenoic acid, methyl 3-pentenoate, 7-octen- 1-al, acrylonitrile, acrylic acid esters, methyl acrylate, methacrylic acid esters, methyl methacrylate, acrolein, allyl alcohol, 3-pentenal, 4-pentenal, and combinations of two or more thereof.
The process of the invention can be illustrated as follow. 
Wherein R8 is H, xe2x80x94CN, xe2x80x94CO2R1, xe2x80x94C(O)NR1R1, xe2x80x94CHO, xe2x80x94OR3, OH, or combinations of two or more thereof; y is an integer from 0 to 12; and x is an integer from 0 to 12. R1 and R3 are the same as those disclosed above
Particularly preferred unsaturated organic compounds are 3-pentenenitrile, 3-pentenoic acid, 3-pentenal, allyl alcohol, and alkyl 3-pentenoate, such as methyl 3-pentenoate, and combinations of two or more thereof. The linear aldehyde compound prepared by the present process starting with one of these compounds can be used advantageously in the preparation of xcex5-caprolactam, hexamethylenediamine, 6-aminocaproic acid, 6-aminocapronitrile or adipic acid, which are precursors for Nylon-6 and/or Nylon-6,6.
The process of the invention also can be carried out with a mixture that comprises two or more unsaturated organic compounds. For example, 3-pentenenitrile can be present in a mixture containing 4-pentenenitrile. Because the 4- isomer reacts in a similar fashion as the corresponding 3-isomer to the desired linear aldehyde, a mixture of isomers can be used directly in the present process.
The 3-pentenenitrile may be present in mixtures containing impurities that do not interfere with the hydroformylation reaction. An example is 2-pentenenitrile.
The hydroformylation process according to the invention can be performed as described below.
The process of the invention can be carried out by any means known to one skilled in the art such as, for example, the one disclosed in U.S. Pat. No. 4,769,498, disclosure of which is incorporated herein by reference. Generally, the process can be carried out under any condition sufficient to effect the production of a desired aldehyde. For example, the temperature can be from about 0xc2x0 C. to 200xc2x0 C., preferably from about 50 to 150xc2x0 C., and more preferably from 85xc2x0 to 110xc2x0 C. The pressure may vary from normal pressure to 5 MPa, preferably from 0.1 to 2 MPa. The pressure is, as a rule, can also be equal to the combined hydrogen and carbon monoxide partial pressures. However, extra inert gases may also be present; the pressure may vary from normal pressure to 15 MPa when inert gases are present. The molar ratio of hydrogen to carbon monoxide is generally between 10:1 and 1:10, and preferably between 6:1 and 1:2.
The amount of transition metal compound is selected so that favorable results can be obtained with respect to catalyst activity and process economy. In general, the concentration of transition metal in the reaction medium, which comprises an unsaturated organic compound, a catalyst composition, and solvent (if present), can be between 10 and 10,000 ppm and more preferably between 50 and 1000 ppm, calculated as free metal.
The molar ratio of the ligand to Group VIII metal is selected so that favorable results can be obtained with respect to catalyst activity and desired aldehdye selectivity. This ratio generally is from about 1 to 100 and preferably from 1 to 20 (moles phosphorus per mole metal).
The solvent may be the mixture of reactants of the hydroformylation reaction itself, such as the starting unsaturated compound, the aldehyde product and/or by-products. Other suitable solvents include saturated hydrocarbons (for example, kerosene, mineral oil, or cyclohexane), ethers (for example, diphenyl ether or tetrahydrofuran), ketones (for example, acetone, cyclohexanone), nitriles (for example, acetonitrile, adiponitrile or benzonitrile), aromatics (for example, toluene, benzene, or xylene), esters (for example, methyl valerate, caprolactone), Texanol(copyright) (Union Carbide), dimethylformamide, or combinationis of two or more thereof.
The hydroformylation process can be run in solution or in the gas phase. When the hydroformylation is carried out in the vapor (gas) phase, the preferred temperature range is from about 50xc2x0 C. to about 180xc2x0 C., most preferably from about 90xc2x0 C. to 110xc2x0 C. The temperature must be chosen so as to maintain all of the reactants and products in the vapor phase, but low enough to prevent deterioration of the catalyst. The particular preferred temperature depends to some extent on the catalyst being used, the olefinic compound being used, and the desired reaction rate. The operating pressure is not particularly critical and can conveniently by from about 0.101 to 1.01 MPa. The pressure and temperature combination must be chosen so as to maintain reactants and products in the vapor phase. A given catalyst is loaded into a reactor, such as a tubular reactor, taking care to avoid exposure of air-sensitive catalysts to O2 from the air. A gaseous mixture of the desired olefinic compound, CO and H2, along with any desired diluent, such as N2, He or Ar, is then passed through the reactor while contacting the catalyst. The reaction products are generally liquid at room temperature and are conveniently recovered by cooling. The reactor effluent can be directly connected to a sampling valve and can be analyzed by gas chromatography. Aldehydic products, such as linear and branched butyraldehydes obtained from hydroformylation of propylene, can be quantitatively separated and analyzed using a 30 M DB-Wax(copyright) capillary GC column.